Ketone aminoindan condensation product



Patented Oct. 1, 1946 UNITED STAT I j KETQNEAMIN omnA CONDENSATION'rnonuo'r Carlin Gibbs, Cuyahoga Fa ls, Ohio, assignor to The B. F.Goodrich Company, New York, N. Y., a corporation of New ,York

' N o Drawing. Application January l1, 1944,

l Serial No. 517,901 pi This invention relates to new compositions ofmatter and pertains more specifically .to the condensation products ofketones. with/aminoindans inwhich th amino group is directly attached tothe aromaticnucleus:

W These new compositions are useful as intermediatesfor the productionof other organic compounds andas antioxidants. They may be used for thepreservation of any organic substances which, tend to deteriorate in thepresence of oxygen, such as fish oils, linseed oil, tung oil, gasolinecontaining unsaturates, rubber, and the like. Theyare effective with anykinds of rubber such as caoutchouc, balata, gutta percha, latex, reclaimed rubber, artificial, rubberisomers, and such syntheticrubbers aspolychloroprene, 00.1 polymers of butadienewith acrylonitrile, styrene,methyl acrylate, methyl methacrylate, isobutylene, and othercopolymerizablemonomers. When used as antioxidants, myrnew compositionsare efiective in amounts ranging from 0.1 to of the materialpto, bepreserved, although larger orsmaller proportions maybe used, dependingupon the particular materialt be-preserved. n

My new composition are prepared by condensing one molecular proportionof a primary aminoindan in which theamino group is directly atsca s.(o1.,260+2s3)* tached to the aromatic nucleus with a ketone in thepresence of an acidic condensation catalyst, with the elimination ofWater. Various substituent groups such asalkyl; alkenyl, aryl, aralkyl,hydroxy,;alkoxy, andaryloxy groups may be prese t'onlthe indan ringinaddition to the amino groups. Among the aminoindan which maybeemployed to form my new composition are 4- aminoindan, 5-aminoindan,l-methyll-aminoindan, Z-methyll-aminoindan, 3-methyl-4-aminoindan,1-methyl-5-aminoindan, 2-methyl-5- aminoindan, 3-methyl-5-aminoindan,4-methyl-- 5-aminoindan, 4-hydroxy-5-aminoindan,1,2-dimethyl-E-aminoindan, 2,2-diethyl-5-aminoindan,1-isopropyl-5-aminoindan, and the like. The. ketones which may beemployed include such compounds as benzophenone, acetophenone, benzoylacetone, dibenzalacetone, hydroxy benzal acetone, benzoin,cyclohexanone, and the like, but preferably the aliphatic ketones suchas acetone, methyl ethyl ketone, acetyl acetone, mesityl oxide,

phorone, .diacetone alcohol, hydroxyacetone, and

the like. I particularly prefer the reaction products of theafore-mentioned aminoindans" with acetone. The acetone neednot be addedas such to the reaction mixture, but may be added in the form of asuitable complex, such as mesityl oxide, phorone, the bisulfite additionproduct of acetone, aceton oxime, or the like, which will decomposeunder the I conditions of the reaction to yield acetone. 7 I

The preparation of my new composition i'scarriedv out by heating amixture of the ketones and the aminoindans in the presence of an acidic"condensation catalyst. Although a diluent or a'sol vent may be added tothe reaction mixture, this procedure i not. necessary. An excess ofeither theaminoindan or the ketone reagent over that required for the.reaction may be employed if desired. The excess reagent may be used assolvent or diluent for the reaction. The reaction may be carried outover a wide temperature range, from about 50 to 200 0., preferably fromto 150 C. and at either atmospheric or elevated Dressuradepending uponthe particular re agents used. Among the catalysts which may be employedare such materials as hydrogen chloride, phosphoric acid, .sulfuric'acid, sodium bisulfate, zinc chloride, aluminum chloride, borontrifiuoride, hydrogen fluoride, stannic chloride, ammonium bromide,iodine, or other materials which either are acids or are capableofliberating acids upon hydrolysis or upon contact with organicsubstances. H y ,7 The following specific examples will serve more fullyto illustrate the nature of my invention;

' Example I The condensation product of E-aminoihdan with acetone wasprepared by heating 39.9 parts by weight of fi-aminoindan together with2.5 parts of hydrochloric acid to a temperature of about C. There wasintroduced into the reaction vessel over a period of about four hours104.4 part of acetone. The reaction mixture was then cooled, and thehydrochloric acid neutralized with a dilute sodium carbonate solution.The oily reaction mixture was then washed with water, and the desiredproduct, which was iormedby the condensation of one molecular proportionof the aminoindan with two molecular proportions of the acetone with theelimination of two molecular proportions of water, was then separatedfrom the excess of unreacted materials by fractional distillation. Theproduct after recrystallization from hexane was a white crystallinesolid melting at 76 to 78 C.

Example II condensation product, which was formed by the condensation ofone molecular proportion of the aminoindan with two molecularproportions of the acetone with the elimination of two molecularproportions of Water, was separated from the solvent and from theunreacted reagent by fractional distillation. The product, alight-colored liquid.

which crystallized on standing, boiled at 102 to 116 C. at 1 mm.

Example III The condensation product of one mol of 4- aminoindan withtwo mols or acetone was prepared by the method described in Example I.Th'eproduct was awhite crystalline solidmelting "at 106 to 108C. I

Although the precise chemical structure of the compounds described inthe specific examples is not known, it is believed that they "aretrimethyl dihydroquinoline derivatives. 7

' My new compositions are far superior in antiojiidant properties to thecondensation products bi ketones with primary aromatic amines previouslyknown. This snperiority is shown by a comparison of the results'obt'ained by using the products of the specific examples asantioxidants i'niubb'er with the results obtained by using thecondensation products of acetone with aniline as an antio'iridant iiithe "same rubber composition.

The renewing rubber cemp'o'sitionfin which the parts are by weight, wasempldyed for the test:

1.. Zinc oxide 5.0 3.0 Carbon black 50.0 Sitea'ric acid 3.5 Pine tar 3.02-inercaptobenz'othiazole r r 1.0 Antioxidant .L' 2.0

Portions of the composition containing various an't'ioikidants' werevulcanized for 60 minutes at 279 F. to produce anoptimu'm cure, and theultimate tensile strength and elongation were measr d before and afteraging the "rubber for 96 hours in oxygen at C. and 300 lbs. per sq. in.The table below shows the loss of tensile strength and elongation afteraging:

' Percent loss Percent de- Antioxidant in tensile crease in strengthelongation None 77 48 Condensation product of one mol of aniline withtwo mols of aceton 51 28 Product of Example I ,33 10 Product of ExampleILL." '32 25 Product of Example I-II 3O 16 Although I have hereindisclosed specific embodiments of my invention, I do not intend to limitmyself solely thereto, but to include all of the obvious variations andmodifications within 1 the spirit and scope of the appended claims.

I claim: 1. The product obtained by condensing a ketone with a primaryaminoindan in the presence 10f an acidic condensation catalyst, saidaminoindan having the amino group directly attached to ac'arbon atom ofthe aromatic ring and having a hydrogen atom attached to at least one ofthe adjacent nuclear aromatic carbon atoms.

2. The product obtained by condensing an ali- .pha'tic ke'tone with aprimary aminoindan in the presence of an 'acidiccondensation catalyst,said aminoindan having the amino group directly attached to a carbonatom of the aromatic ring and having a hydrogen atom attached to atleast one of the adjacent nuclear aromatic carbon atoms.

3. The product obtained by condensing acetone with a primary aminoindanin the presence of an acidic condensation catalyst, said aminoindanhaving the amino group directly attached to 'a carbon atom or thearomatic ring and having a adjacent nuclear aromatic carbon atoms.

4. The product obtained by condensing 4- aminoindan with a ketone in thepresence of an acidic condensaticn catalyst.

5."The product 'ebta'i-ned by condensing '4'- a'ininoindan with analiphatic keto'ne in the presence or an acidiceondenSatien catalyst.

6. The product ob'tained by condensing 4- aminoinclan with acetone inthe presence of an acidic condensation eatalys't.

7-. The product obtained by condensing 5- ammemcan with a' ketone in the"presence of an acidic condensation catawst.

'8, The product ebtained by condensing 5- aminoindan with an aliphaticketo'ne 'in the resence of an acidic condensation catalyst.

9. The prccuet obtained by condensing 5- am-ineindan with acetone m thepresence of an acidic cdndensatien catalyst.

e-ARmN F. (nines.

